CN115872415B - Nano ZSM-5 molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of molecular sieve synthesis, and provides a nano ZSM-5 molecular sieve and a preparation method thereof. The preparation method of the nano ZSM-5 molecular sieve comprises the following steps: s1, mixing a template agent, an aluminum source, a silicon source, a dispersing agent, metal salt, alkali and water, and performing pre-crystallization to obtain a pre-crystallization liquid; s2, mixing an aluminum source, a silicon source, a guiding agent and water to obtain a homogeneous gel; s3, mixing the pre-crystallized liquid with the homogeneous gel, and crystallizing to obtain the nano ZSM-5 molecular sieve. The nanometer ZSM-5 molecular sieve is prepared by the method. By the technical scheme, the problems that the ZSM-5 molecular sieve in the prior art has low catalytic activity or weak shape selective cracking capability and can not improve the shape selective cracking and aromatization functions of the catalyst/auxiliary agent simultaneously are solved.
Description
Technical Field
The invention relates to the technical field of molecular sieve synthesis, in particular to a nano ZSM-5 molecular sieve and a preparation method thereof.
Background
With the rapid development of the oil refining industry, the demand for low-carbon olefins and aromatics is rapidly increasing. The average increase in consumption of finished oil such as global gasoline, kerosene and diesel oil in 2017 is 2.1%, and the average increase in consumption of ethylene, propylene, butylene, benzene and xylene is 5.6%. From 2018 to 2026, the global gasoline demand composite annual average growth rate will be lower than 1%, but propylene growth is up to 4%.
Since the first report of ZSM-5 molecular sieve synthesis by the American Mobil company in 1972 (USP 3702886), it has been widely used because of its unique three-dimensional pore structure which shows high activity, high stability and high selectivity. ZSM-5 is an important active component of the shape selective catalytic reaction, and has strong acidity and good hydrothermal stability, and obvious advantages for cracking medium and small molecules. Therefore, various process technologies for producing low-carbon olefin based on ZSM-5 catalytic reaction are developed at home and abroad, wherein propylene production by a Fluid Catalytic Cracking (FCC) process has the characteristics of low investment, wide raw material adaptability, low cost and the like, and is highly concerned.
The conventional ZSM-5 zeolite is generally adopted as a shape selective cracking active component in the prior art for producing the low-carbon olefin catalyst/auxiliary agent, but the ZSM-5 zeolite belongs to microporous zeolite, and has smaller pore channel size, so that the catalysis of macromolecular reactants is limited to a certain extent. At present, two improved methods are mainly adopted, namely, a mesoporous structure (such as CN101003380B, CN 104340991B) is introduced into a ZSM-5 zeolite micropore structure to form a diffusion pore canal which is beneficial to macromolecules; and secondly, synthesizing the superfine ZSM-5 molecular sieve (such as CN102001680B, CN 102502696B) with nanometer scale.
The existing hierarchical pore ZSM-5 molecular sieve is low in catalytic activity due to weak acidity, and the nano ZSM-5 molecular sieve is low in shape selective cracking capability even though the catalytic activity is high, so that the shape selective cracking and aromatization functions of the catalyst/auxiliary agent cannot be improved simultaneously. Therefore, it is a technical problem to be solved by those skilled in the art to provide a ZSM-5 molecular sieve capable of greatly improving the yield of low-carbon olefins and the aromatic hydrocarbon content of gasoline in catalytic cracking reaction.
Disclosure of Invention
The invention provides a nano ZSM-5 molecular sieve and a preparation method thereof, which solve the problems that the ZSM-5 molecular sieve in the related art has low catalytic activity or weak shape selective cracking capability and can not improve the shape selective cracking and aromatization functions of a catalyst/an auxiliary agent at the same time.
The technical scheme of the invention is as follows:
the preparation process of nanometer ZSM-5 molecular sieve includes the following steps:
s1, mixing a template agent, an aluminum source, a silicon source, a dispersing agent, metal salt, alkali and water, and performing pre-crystallization to obtain a pre-crystallization liquid;
s2, mixing an aluminum source, a silicon source, a guiding agent and water to obtain a homogeneous gel;
s3, mixing the pre-crystallized liquid with the homogeneous gel, and crystallizing to obtain the nano ZSM-5 molecular sieve.
As a further technical scheme, in S1, the mass ratio of the template agent, the aluminum source, the silicon source, the dispersing agent, the metal salt, the alkali and the water is 1-20:1:10-75:0.01-2.5:0.0003-2:0.01-10:15-300.
As a further technical scheme, in the S1, the pre-crystallization temperature is 80-250 ℃, and the pre-crystallization time is 10-30 hours.
As a further technical scheme, the template agent comprises one or more of tetraethylammonium hydroxide, tetrapropylammonium bromide, triethylamine, diethylammonium and ammonia water;
and/or, the aluminum source in S1 and the aluminum source in S2 each independently comprise one or more of pseudo-boehmite, aluminum sulfate, aluminum nitrate and aluminum chloride;
and/or, the silicon source in S1 and the silicon source in S2 each independently comprise one or more of white carbon black, silicone grease, silica gel, silica sol and water glass;
and/or the dispersing agent comprises one or more of polyacrylamide, aminopropyl trimethoxysilane, amino trimethoprim, cellulose and sodium pyrophosphate;
and/or the metal salt comprises one or more of rare earth chloride, rare earth nitrate, ferric chloride, silver nitrate, zinc nitrate and zinc chloride;
and/or, the base comprises sodium hydroxide or n-butylamine;
and/or the guiding agent comprises one or more of sodium hydroxide, sodium metaaluminate and water glass.
As a further technical scheme, in the S2, the mass ratio of the aluminum source to the silicon source to the guiding agent to the water is 1:20-150:0.5-8:15-1000.
As a further technical scheme, in the S3, the mass ratio of the pre-crystallization liquid to the homogeneous gel is 0.3-12:100.
As a further technical scheme, in the step S3, the crystallization temperature is 80-250 ℃, and the crystallization time is 5-50 h.
As a further technical scheme, in S3, before crystallization, the pre-crystallized solution is mixed with the homogeneous gel, and the obtained mixed solution is aged for 5-30 hours at room temperature.
As a further technical scheme, in S3, filtering and drying are further included after crystallization.
The nanometer ZSM-5 molecular sieve is prepared according to the preparation method, and the specific surface area of the nanometer ZSM-5 molecular sieve is 250-550 m 2 The micropore volume per gram is 0.20-0.45 mL/g, the mesopore volume is 0.10-0.25 mL/g, the grain size is 30-300 nm, and the silicon-aluminum ratio is 15-150.
The working principle and the beneficial effects of the invention are as follows:
the nano ZSM-5 molecular sieve provided by the invention is used for catalytic cracking/cracking reaction, so that the shape selective cracking reaction activity is greatly improved, and the cracking capability of straight-chain olefins and isoparaffins in gasoline is obviously enhanced, and meanwhile, due to the existence of multiple stages of pore channels, certain low-carbon olefin aromatization capability is shown, so that the propylene yield, the gasoline octane number and the propylene concentration in liquefied gas are obviously increased.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an SEM morphology of ZAP-5 nm ZSM-5 molecular sieve prepared in example 1 of the present invention;
FIG. 2 is an SEM morphology of a DB-4 comparative nano ZSM-5 molecular sieve prepared in comparative example 1;
FIG. 3 is an SEM morphology of a conventional ZSM-5 molecular sieve of comparative example 2 NK-1;
FIG. 4 is an XRD characterization of ZAP-5 nano ZSM-5 molecular sieve prepared in example 1 of the present invention, DB-4 comparative nano ZSM-5 molecular sieve prepared in comparative example 1, and conventional ZSM-5 molecular sieve of comparative example 2 NK-1;
FIG. 5 is a schematic representation of NH of ZAP-5 nano ZSM-5 molecular sieve prepared in example 1 of the present invention, DB-4 comparative nano ZSM-5 molecular sieve prepared in comparative example 1, and conventional ZSM-5 molecular sieve of comparative example 2 NK-1 3 -TPD。
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials used in the following examples and comparative examples were as follows (weight percentages unless indicated as industrial):
tetrapropylammonium hydroxide: concentration 25%; tetrapropylammonium bromide, solid; n-butylamine, liquid; silica sol: siO (SiO) 2 40% Density 1.31g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the White carbon black: siO (SiO) 2 99 percent; sodium metaaluminate: al (Al) 2 O 3 50g/L，Na 2 O content is 100g/L; boehmite (boehmite): 71% of solid content; pseudo-boehmite: the solid content is 66%; aluminum sol: al (Al) 2 O 3 23.5%; phosphoric acid 85%; 98% of sulfuric acid; kaolin: solid content 85.8%, fe 2 O 3 0.3%，TiO 2 0.2%, average particle size 3.5 μm; rare earth chloride, silver nitrate, zinc nitrate and zinc chloride are all industrial products.
The analytical test method is as follows:
1. ZSM-5 crystallinity: an X-ray diffraction method is adopted to respectively measure the sum of peak areas of five characteristic diffraction peaks of XRD patterns 2 theta of the sample and the standard sample between 22.5 and 25 degrees, wherein the percentage value is the content of ZSM-5; the standard sample is selected from a high-quality ZSM-5 molecular sieve produced by Nankan, and the crystallinity of the high-quality ZSM-5 molecular sieve is determined to be 95%;
2. elemental composition and silicon to aluminum ratio: XRF fluorescence;
3. solid content: burning, 800 ℃/1 hour;
4. average particle size: laser particle size analyzer method;
5. and (3) crystal grains: SEM electron microscope analysis;
6. specific surface area and pore volume: nitrogen adsorption;
7. solid acid distribution: NH (NH) 3 TPD analysis.
Example 1
S1, preparing a pre-crystallization liquid: 1000g of deionized water, 200g of tetrapropylammonium bromide, 2.5g of rare earth chloride, 0.5g of zinc chloride, 12g (based on dry basis) of boehmite and 62g of NaOH are added into a reaction kettle, after stirring for 5min, 400g (based on dry basis) of white carbon black and 30g of polyacrylamide are slowly added, so that colloid keeps fluidity all the time, the colloid is continuously stirred vigorously for 1.5h, and is transferred into a high-pressure crystallization kettle, heated to 180 ℃ and crystallized for 20h, and a pre-crystallization liquid is obtained;
s2, preparing a homogeneous gel: 1500g of deionized water, 25g (based on dry basis) of boehmite and 68g of NaOH are added into a reaction kettle, and after stirring for 5min, 500g (based on dry basis) of white carbon black is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 80g of pre-crystallization liquid, continuing to stir vigorously for 1.5h, aging for 10h at room temperature, transferring into a high-pressure crystallization kettle, heating to 175 ℃, crystallizing for 20h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 88 percent, and the specific surface area is 400m 2 Per gram, the micropore volume is 0.32mL/g, the mesopore volume is 0.19mL/g, the grain size is 100nm, and the silicon-aluminum ratio is 45.
Example 2
S1 is the same as S1 in example 1;
s2, preparing a homogeneous gel: 1130g of deionized water, 7.5g (based on dry basis) of pseudo-boehmite and 450mL of sodium metaaluminate are added into a reaction kettle, and after stirring for 5min, 450g (based on dry basis) of white carbon black is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 110g of pre-crystallization liquid, continuing to stir vigorously for 2h, aging for 5h at room temperature, transferring into a high-pressure crystallization kettle, heating to 160 ℃, crystallizing for 25h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 90 percent, and the specific surface area is 385m 2 Per gram, the micropore volume is 0.30mL/g, the mesopore volume is 0.18mL/g, the grain size is 150nm, and the silicon-aluminum ratio is 27.
Example 3
S1, preparing a pre-crystallization liquid: 600g of tetrapropylammonium hydroxide (content of 25%) solution, 130g of n-butylamine, 0.3g of silver nitrate, 1g of zinc nitrate and 16g (based on dry basis) of pseudo-boehmite are added into a reaction kettle, after stirring for 5min, 1200g of silica sol and 15g of amino trimethoprim are slowly added, and the mixture is continuously and vigorously stirred for 2h, and is transferred into a high-pressure crystallization kettle, and the temperature is raised to 160 ℃ for crystallization for 15h, so as to obtain a pre-crystallization liquid;
s2, preparing a homogeneous gel: 250g of deionized water, 16g (based on dry basis) of boehmite and 75g of NaOH are added into a reaction kettle, after stirring for 5min, 1600mL of silica sol is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 80g of pre-crystallization liquid, continuing to stir vigorously for 1.5h, aging for 30h at room temperature, transferring into a high-pressure crystallization kettle, heating to 200 ℃, crystallizing for 30h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 85 percent, and the specific surface area is 400m 2 Per gram, the micropore volume is 0.32mL/g, the mesopore volume is 0.19mL/g, the grain size is 80nm, and the silicon-aluminum ratio is 65.
Example 4
S1 is the same as S1 in example 3;
s2, preparing a homogeneous gel: 1150g of deionized water, 6g (based on dry basis) of pseudo-boehmite and 480mL of sodium metaaluminate are added into a reaction kettle, and after stirring for 5min, 580g (based on dry basis) of white carbon black is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 110g of pre-crystallization liquid, continuously stirring vigorously for 2 hours, transferring into a high-pressure crystallization kettle, heating to 180 ℃, crystallizing for 25 hours, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 91 percent, and the specific surface area is 410m 2 Per gram, the micropore volume is 0.29mL/g, the mesopore volume is 0.17mL/g, the grain size is 100nm, and the silicon-aluminum ratio is 34.
Example 5
S1, preparing a pre-crystallization liquid: 400g of tetrapropylammonium hydroxide (content of 25%) solution, 80g of tetrapropylammonium bromide, 20g of n-butylamine, 0.6g of silver nitrate and 20g (based on dry basis) of pseudo-boehmite are added into a reaction kettle, after stirring for 5min, 1400g of silica sol and 35g of sodium pyrophosphate are slowly added, and the mixture is continuously and vigorously stirred for 1h, and is transferred into a high-pressure crystallization kettle, heated to 200 ℃ and crystallized for 30h, so as to obtain a pre-crystallized liquid;
s2, preparing a homogeneous gel: 250g of deionized water, 16g (based on dry basis) of boehmite and 70g of NaOH are added into a reaction kettle, after stirring for 5min, 1400mL of silica sol is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 90g of pre-crystallization liquid, continuously stirring vigorously for 1.5h, transferring into a high-pressure crystallization kettle, heating to 200 ℃, crystallizing for 28h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 90 percent, and the specific surface area is 380m 2 Per gram, the micropore volume is 0.33mL/g, the mesopore volume is 0.18mL/g, the grain size is 180nm, and the silicon-aluminum ratio is 60.
Example 6
S1, preparing a pre-crystallization liquid: adding 3600g deionized water, 12g tetrapropylammonium bromide, 0.003g rare earth chloride, 0.0006g zinc chloride, 12g (calculated on a dry basis) boehmite and 120g NaOH into a reaction kettle, stirring for 5min, slowly adding 150g (calculated on a dry basis) white carbon black and 0.12g polyacrylamide, keeping the colloid flowing all the time, continuing to vigorously stir for 1.5h, transferring into a high-pressure crystallization kettle, heating to 80 ℃, and crystallizing for 30h to obtain a pre-crystallization liquid;
s2, preparing a homogeneous gel: 2500g of deionized water, 25g (based on dry basis) of boehmite and 12.5g of NaOH are added into a reaction kettle, after stirring for 5min, 1750g (based on dry basis) of white carbon black is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 12.8g of pre-crystallization liquid, continuing to stir vigorously for 1.5h, aging for 5h at room temperature, transferring into a high-pressure crystallization kettle, heating to 80 ℃, crystallizing for 50h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 95 percent, and the specific surface area is 500m 2 Per gram, the micropore volume is 0.41mL/g, the mesopore volume is 0.23mL/g, the grain size is 220nm, and the silicon-aluminum ratio is 120.
Example 7
S1, preparing a pre-crystallization liquid: 180g of deionized water, 240g of tetrapropylammonium bromide, 20g of rare earth chloride, 4g of zinc chloride, 12g (calculated on a dry basis) of boehmite and 0.12g of NaOH are added into a reaction kettle, after stirring for 5min, 900g (calculated on a dry basis) of white carbon black and 30g of polyacrylamide are slowly added, so that colloid keeps fluidity all the time, the colloid is continuously and vigorously stirred for 1.5h and is transferred into a high-pressure crystallization kettle, the temperature is raised to 250 ℃, and crystallization is carried out for 10h, thus obtaining pre-crystallization liquid;
s2, preparing a homogeneous gel: 25000g of deionized water, 25g (based on dry basis) of boehmite and 200g of NaOH are added into a reaction kettle, after stirring for 5min, 2200g (based on dry basis) of white carbon black is slowly added to obtain homogeneous gel;
s3, preparing a molecular sieve: and (3) keeping fluidity of the homogeneous gel obtained in the step (S2) all the time, adding 3477g of pre-crystallized liquid, continuing to stir vigorously for 1.5h, aging for 30h at room temperature, transferring into a high-pressure crystallization kettle, heating to 250 ℃, crystallizing for 5h, and then filtering, washing and drying to obtain the nano ZSM-5 molecular sieve (ZAP-5).
The analysis test shows that the relative crystallinity of the nanometer ZSM-5 molecular sieve (ZAP-5) is 78 percent, the specific surface area is300m of 2 Per gram, the micropore volume is 0.27mL/g, the mesopore volume is 0.15mL/g, the grain size is 50nm, and the silicon-aluminum ratio is 150.
Comparative example 1
104g of silica sol is dispersed in 40g of deionized water, 7.0g of NaOH is added, high-speed stirring is carried out for 1h, and 14.9g of n-butylamine is added to prepare solution A;
dispersing 2.3g of pseudo-boehmite in 100g of deionized water, then adding 5g of 98% sulfuric acid, and stirring at a high speed for 1h to prepare a solution B;
adding the solution B into the solution A to prepare homogeneous gel, transferring into a high-pressure crystallization kettle, heating to 170 ℃, crystallizing for 20 hours, cooling, filtering, washing and drying to obtain the comparative nano ZSM-5 molecular sieve (DB-4).
The analysis test shows that the relative crystallinity of the comparative nano ZSM-5 molecular sieve (DB-4) is 78 percent, and the specific surface area is 380m 2 Per gram, the micropore volume is 0.34mL/g, the mesopore volume is 0.09mL/g, the grain size is 90nm, and the silicon-aluminum ratio is 29.
Comparative example 2
Conventional ZSM-5 molecular sieve (NK-1), silicon-aluminum ratio of 40, relative crystallinity of 88% and solid content of 96.0%.
Preparing an auxiliary agent: the molecular sieves provided in example 1 and comparative examples 1-2 were prepared as adjuvants by the following method: 770g of deionized water, 468g of kaolin and 162g of phosphoric acid are sequentially added into a reaction kettle, pulping is carried out for 1h, 426g of aluminum sol and 500g of molecular sieve (dry basis) are added, pulping is carried out for 0.5h, high-speed shearing is carried out for 50min, spray drying forming is carried out, and microspheres are roasted for 1h at 500 ℃, thus obtaining the auxiliary agent.
Performance test: the auxiliaries obtained in example 1 and comparative examples 1 to 2 and a CC-20D industrial catalyst (main catalyst) were treated at 800℃under 100% steam conditions for 17 hours, respectively, and then the main catalyst was prepared by: adjuvant = 90:10 mix. The cracking reaction is carried out in a ACE (Advanced Catalytic Evaluation) fixed fluidized bed reactor under the conditions of 9g of catalyst loading, 6 of catalyst-to-oil ratio, 527 ℃ of reaction temperature and 8h of weight space velocity -1 The properties of the raw oil are shown in Table 1, and the samples of the main catalyst and the compounding auxiliary agent are compared and evaluated according to the following formulaThe conversion, total liquid yield and propylene concentration were calculated by the following formula:
conversion (wt%) =dry gas (wt%) +liquefied gas (wt%) +gasoline (wt%) +coke (wt%)
Total liquid yield (wt%) =liquefied gas (wt%) +gasoline (wt%) +diesel (wt%)
Propylene concentration (%) =propylene yield/liquefied gas yield×100%;
the results are shown in Table 2.
TABLE 1 Properties of raw oil
TABLE 2 comparative evaluation of Primary catalyst and Primary catalyst+auxiliary
As can be seen from Table 2, the catalyst of the auxiliary agent prepared by the molecular sieve of the invention can greatly improve the propylene yield and the propylene concentration in the liquefied gas and obviously increase the aromatic hydrocarbon content and the octane number of the gasoline due to the effective cracking of the low-octane isoparaffin and other low-octane components in the catalytic cracking reaction. The nano molecular sieve provided by the invention has excellent shape selective cracking performance and a certain aromatization function, and has good application prospect in the transition development of the refining industry.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (2)
1. The application of the nano ZSM-5 molecular sieve in the catalytic cracking reaction is characterized in that the preparation method of the nano ZSM-5 molecular sieve comprises the following steps:
s1, mixing a template agent, an aluminum source, a silicon source, a dispersing agent, metal salt, alkali and water, and performing pre-crystallization to obtain a pre-crystallization liquid;
s2, mixing an aluminum source, a silicon source, a guiding agent and water to obtain a homogeneous gel;
s3, mixing the pre-crystallized liquid with the homogeneous gel, and crystallizing to obtain the nano ZSM-5 molecular sieve;
in the step S1, the pre-crystallization temperature is 80-250 ℃ and the pre-crystallization time is 10-30 hours;
the specific surface area of the nano ZSM-5 molecular sieve is 250-550 m 2 Per gram, the micropore volume is 0.20-0.45 mL/g, the mesopore volume is 0.10-0.25 mL/g, the grain size is 30-300 nm, and the silicon-aluminum ratio is 15-150;
in the S1, the mass ratio of the template agent, the aluminum source, the silicon source, the dispersing agent, the metal salt, the alkali and the water is 1-20:1:10-75:0.01-2.5:0.0003-2:0.01-10:15-300;
the template agent comprises tetrapropylammonium bromide;
the aluminum source in S1 and the aluminum source in S2 respectively and independently comprise one or more of pseudo-boehmite, aluminum sulfate, aluminum nitrate and aluminum chloride;
the silicon source in S1 and the silicon source in S2 respectively and independently comprise one or more of white carbon black, silicone grease, silica gel, silica sol and water glass;
the dispersant comprises polyacrylamide;
the metal salt comprises rare earth chloride and zinc chloride;
the base includes sodium hydroxide;
the guiding agent comprises sodium hydroxide;
in the S2, the mass ratio of the aluminum source to the silicon source to the guiding agent to the water is 1:20-150:0.5-8:15-1000;
in the step S3, the mass ratio of the pre-crystallization liquid to the homogeneous gel is 0.3-12:100;
in the step S3, the crystallization temperature is 80-250 ℃, and the crystallization time is 5-50 h;
in the step S3, before crystallization, the pre-crystallization liquid and the homogeneous gel are mixed, and the obtained mixed liquid is aged for 5-30 hours at room temperature.
2. The use of a nano ZSM-5 molecular sieve according to claim 1, wherein in S3, the crystallization is followed by filtration and drying.
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